CN114479266B - Folding-resistant polypropylene composite material and preparation method and application thereof - Google Patents
Folding-resistant polypropylene composite material and preparation method and application thereof Download PDFInfo
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- CN114479266B CN114479266B CN202111575782.8A CN202111575782A CN114479266B CN 114479266 B CN114479266 B CN 114479266B CN 202111575782 A CN202111575782 A CN 202111575782A CN 114479266 B CN114479266 B CN 114479266B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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Abstract
The invention discloses a folding-resistant polypropylene composite material, and a preparation method and application thereof, and belongs to the technical field of high polymer materials. The folding-resistant polypropylene composite material comprises the following components in parts by weight: 40-60 parts of metallocene polypropylene; 10-30 parts of impact copolymer polypropylene; 20-30 parts of filler; 5-10 parts of thermoplastic elastomer; 0-3 parts of auxiliary agent; the molecular weight distribution index Mw/Mn of the metallocene polypropylene is 2.3-2.7, the crystallinity is 32-38%, and the test standard of the crystallinity is ISO 11357-2016; the molecular weight distribution index Mw/Mn of the impact copolymer polypropylene is 3.9-4.4, the crystallinity is 31-37%, and the mass content of the ethylene propylene rubber in the impact copolymer polypropylene is 15-30%. The folding-resistant polypropylene composite material provided by the invention can improve the breaking elongation of a hinge structure workpiece, and can not crack after repeatedly folding the surface layer, so that the folding-resistant polypropylene composite material has a good appearance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a folding-resistant polypropylene composite material, a preparation method thereof, application of the folding-resistant polypropylene composite material in preparation of plastic hinges and the plastic hinges.
Background
The polypropylene (PP) material has very good stress cracking resistance and very high bending fatigue life, and is also a reason for commonly called 'hundred-fold glue' of the polypropylene material. The polypropylene material can be used for preparing hinge structure parts for connecting two matrixes, such as snack boxes, washing article covers, storage box covers, traveling cases, automobile parts and the like, and the hinge structure parts can be folded at an angle of approximately 180 degrees, and the folding times can reach 700 ten thousand times.
The polypropylene material for preparing the hinge structure parts adopts homo-polypropylene, co-polypropylene and random polypropylene as a matrix, and inorganic rigid particles and polyolefin thermoplastic elastomer are added, so that the balance of rigidity and toughness can be achieved after injection molding of parts, and the multi-fold non-cracking can be realized.
The prior art discloses a folding-resistant polypropylene composite material which is used for preparing automobile parts such as automobile fuse boxes and the like with hinge structures, metallocene elastomers are added into homo-polypropylene and co-polypropylene to serve as toughening agents to improve the folding resistance of polypropylene at low temperature and under mineral filling, and inorganic fillers are added to improve rigidity. However, due to the addition of the rubber phase of the metallocene elastomer and the rigid particles of the inorganic filler, various heterogeneous components appear in the polypropylene material, and stress defect points of the hinge structural part prepared from the material appear gradually increase in the repeated folding process, so that the surface layer of the part can be broken after the repeated folding. In addition, the elongation at break is only 260-300%, and the requirement of higher elongation at break cannot be met.
Disclosure of Invention
The invention aims to overcome the defects that the surface layer of the existing folding-resistant polypropylene composite material is easy to crack and low in elongation at break, and provides the folding-resistant polypropylene composite material, the elongation at break of the folding-resistant polypropylene composite material is effectively improved through the synergistic effect of metallocene polypropylene and impact-resistant copolymerized polypropylene, and after the folding-resistant polypropylene composite material is prepared into a hinge structural part, the surface layer cannot crack after repeated folding.
The invention also aims at providing a preparation method of the folding-resistant polypropylene composite material.
Another object of the invention is to provide the use of a fold-resistant polypropylene composite for the preparation of plastic hinges.
It is a further object of the present invention to provide a plastic hinge.
The above object of the present invention is achieved by the following technical scheme:
the folding-resistant polypropylene composite material comprises the following components in parts by weight:
wherein the metallocene polypropylene has a molecular weight distribution index M w /M n 2.3 to 2.7, the crystallinity is 32 to 38 percent, and the test standard of the crystallinity is ISO 11357-2016;
molecular weight distribution index M of the impact copolymer polypropylene w /M n 3.9 to 4.4, the crystallinity is 31 to 37 percent, the test standard of the crystallinity is ISO 11357-2016, and the mass content of the ethylene propylene rubber in the impact copolymer polypropylene is 15 to 30 percent.
Molecular weight distribution index M w /M n Is an index for indicating the degree of dispersion of the molecular weight distribution, M w Is the weight average molecular weight, M n Is the number average molecular weight.
The method for testing the mass content of the ethylene propylene rubber in the impact copolymer polypropylene comprises the following steps: the sample was dissolved in 98% n-decane, extracted at 145℃in a flask equipped with a reflux unit, cooled to room temperature, the rubber phase was dissolved in n-decane, and the remainder was crystallized and filtered. And then adding acetone into the filtrate to separate out the rubber phase in the filtrate, filtering, drying, weighing and calculating the content of the rubber phase.
The following are to be described:
the folding-resistant polypropylene composite material can realize the improvement of the elongation at break through the optimized synergistic effect of the resin base material, does not influence other physical and mechanical properties, can not crack when repeatedly folding the surface layer in the continuous use process of the hinge structure workpiece, and has good appearance. On the basis of keeping the balance between rigidity and toughness, the rigidity of the composite material is improved to a certain extent.
The action mechanism of each component of the folding-resistant polypropylene composite material is as follows:
molecular weight distribution index M of metallocene polypropylene w /M n 2.3 to 2.7, the crystallinity is 32 to 38 percent, and the molecular weight distribution is narrower, the degree of intertwining between molecular chains is high, and the crystallinity is low; impact copolymer polypropylene molecular weight distribution index M w /M n 3.9 to 4.4, the crystallinity is 31 to 37 percent, the mass content of ethylene propylene rubber in the impact copolymer polypropylene is 15 to 30 percent, and the impact copolymer polypropylene has the characteristics of wider molecular weight distribution, lower crystallinity and high rubber content.
The invention takes the metallocene polypropylene as a main matrix, and fully utilizes the characteristics of narrow molecular weight distribution and high degree of intertwining between molecular chains of the metallocene polypropylene material. In injection molding, when the metallocene polypropylene forms a hinge structure with smaller thickness, the winding degree among molecular chains is higher, the orientation degree is weaker, and the metallocene polypropylene molecular chains are less prone to obvious stretching phenomenon, so that the metallocene polypropylene can keep the original structure form when repeatedly folded in the later period, and the surface breakage is avoided.
Meanwhile, the lubricating and steric hindrance effects of the impact copolymer polypropylene with wider molecular weight distribution in melt flow are reduced, the material melt can be smoothly injection-molded into a hinge structure with the thickness narrowed from wide, and the injection-moldability of the composite material is improved.
The metallocene polypropylene and the impact copolymer polypropylene are used as the matrix together, the crystallinity of the metallocene polypropylene and the impact copolymer polypropylene is low, the degree of the crystallization area being destroyed and translated is naturally low when the hinge is repeatedly folded, and the degree of winding of the molecular chain is high, so that the elongation at break can be improved, and the effect that the surface layer is folded without breaking can be achieved.
For the polypropylene composite material of the injection molding hinge structure, the ethylene propylene rubber state in the surface layer plays a role in breaking elongation at the same time, when the surface layer is in a stretching and bending state, the ethylene propylene rubber phase of the impact copolymer polypropylene plays a role in synchronously stretching and bending, and the ethylene propylene rubber phase can bear larger stretching and bending deformation, so that the breaking elongation of the composite material is better in macroscopic appearance.
The thermoplastic elastomer has lower crystallinity, plays a role of a rubber phase, reduces the crystallinity of the whole material to a certain extent, and is favorable for improving the tensile elongation at break.
When the mass content of ethylene propylene rubber in the impact copolymer polypropylene is lower than 15%, the elongation at break cannot be improved.
When the mass content of the ethylene propylene rubber in the impact copolymer polypropylene is higher than 30%, the improvement of the elongation at break is facilitated, but the balance of the overall rigidity and the toughness of the composite material is affected.
The filler is used for improving the rigidity of the material, the thermoplastic elastomer is used for improving the toughness of the material, and the filler and the thermoplastic elastomer can be controlled to achieve the balance between the rigidity and the toughness within the scope of the invention.
Preferably, the method comprises the steps of,
the composite material comprises the following components in parts by weight:
the auxiliary agent is one or more of antioxidant, lubricant or toner.
The proportion of the metallocene polypropylene and the impact copolymer polypropylene is kept at a proper proportion, and the effect is not good too high or too low, when the proportion of the metallocene polypropylene is 45-50 parts and the proportion of the impact copolymer polypropylene is 25-28 parts, the surface layer is effectively prevented from cracking after folding and the elongation at break is improved when the proportion of the metallocene polypropylene and the impact copolymer polypropylene is kept at 1 (0.4-0.6).
The thermoplastic elastomer has the function of improving the toughness of the material, and is less than 6 parts, and the toughness of the thermoplastic elastomer is poor; the addition of 7 parts or more improves the toughness of the material, but makes the material too soft, resulting in a decrease in rigidity.
The content of the filler is related to the rigidity of the final material, the addition amount is less than 25 parts, and the filler has no obvious effect of improving the rigidity of the material; when the amount exceeds 28 parts, the rigidity is remarkably improved, but breakage is likely to occur.
Preferably, the crystallinity of the metallocene polypropylene is 34 to 36%.
The lower the crystallinity of the metallocene polypropylene is, the higher the content of the polypropylene molecular chains in an amorphous form is, and the degree of the destruction and translation of a crystallization area is naturally lower when the polypropylene is repeatedly folded, so that the winding degree of the molecular chains is high, and the elongation at break can be improved. Metallocene polypropylene has crystallinity below 34% but can have a negative impact on the stiffness of the material.
Preferably, the crystallinity of the impact copolymer polypropylene is 32-35%, and the mass content of the ethylene propylene rubber in the impact copolymer polypropylene is 25-30%.
The impact copolymer polypropylene has lower crystallinity, and the content of the polypropylene molecular chain in an amorphous form is improved, and the polypropylene molecular chain is entangled with the metallocene polypropylene in repeated folding, so that the elongation at break can be improved. Metallocene polypropylene has crystallinity lower than 32% but can have a negative impact on the stiffness of the material.
The mass content of ethylene propylene rubber in the impact copolymer polypropylene is higher, the rubber phase content of the surface layer of the hinge is higher, and the stretching and bending deformation borne by the impact copolymer polypropylene is further improved, so that the elongation at break of the composite material is improved. Ethylene propylene rubber in impact copolymer polypropylene above 30% can negatively impact the stiffness of the material.
Preferably, the mass melt mass flow rate of the metallocene polypropylene is 20-30 g/10min, the test standard is ISO1133-2011, and the test condition is 230 ℃ and 2.16kg.
The metallocene polypropylene has higher melt mass flow rate, is beneficial to the hinge structure with narrowed thickness, and prevents obvious molecular chain stretching phenomenon from happening when passing through the hinge structure.
When the mass flow rate of the melt is lower than 20g/10min, the composite material is not beneficial to pass through a cavity with the thickness of only 0.2-0.5 mm, a more remarkable molecular chain stretching orientation phenomenon can appear, and the phenomena of obvious crease whitening, surface layer cracks and the like appear when the hinge structure is repeatedly folded are shown.
When the melt mass flow rate is higher than 30g/10min, the molecular weight distribution of the metallocene polypropylene is narrow, and the molecular weight distribution of the polymer are the main influences on the melt mass flow rate, when the melt mass flow rate is higher, the molecular weight of the polypropylene naturally decreases, and although the smooth passing property of the modified composite material when passing through a hinge structure is obviously improved, the molecular weight of the main component is obviously reduced, and the impact property of the modified composite material is obviously reduced.
Still more preferably, the metallocene polypropylene has a flexural modulus of 1200 to 1600MPa and a test standard of ISO178-2010; the cantilever beam notch impact strength of the metallocene polypropylene is 2-10 kJ/m 2 The test standard is ISO180-2000, and the test temperature is 23 ℃.
The bending modulus of the metallocene polypropylene is 1200-1600 MPa, and the notch impact strength of the cantilever beam is 2-10 kJ/m 2 The balance of rigidity and toughness can be achieved, so that the final material can also achieve the balance of rigidity and toughness.
Preferably, the impact-resistant copolymerized polypropylene has a notched Izod impact strength of 30-50 kJ/m 2 The test standard is ISO180-2000, and the test temperature is 23 ℃.
The rubber content of the impact-resistant copolymerized polypropylene is higher, and the notch impact strength of the cantilever beam is 30-50 kJ/m 2 Has higher impact resistance.
Still more preferably, the impact copolymer polypropylene has a melt mass flow rate of 10 to 30g/10min, with test standard ISO1133-2011; the flexural modulus of the impact copolymer polypropylene is 800-1600 MPa, and the test standard is ISO178-2010.
The flexural modulus of the impact copolymer polypropylene is 800-1600 MPa, and the notch impact strength of the cantilever beam is 30-50 kJ/m 2 The balance of rigidity and toughness can be realized, and the balance of rigidity and toughness can be realized by the final material when the material is used together with metallocene polypropylene.
Preferably, the thermoplastic elastomer is an ethylene-octene copolymer, the thermoplastic elastomer has a crystallinity of 3 to 6% and the test standard for crystallinity is ISO 11357-2016.
For the crystalline ethylene-octene copolymer, the crystallinity is generally 8-10% as measured by DSC method, and for the amorphous ethylene-octene copolymer, the crystallinity is generally 3-6% as measured by DSC method, the invention adopts the amorphous ethylene-octene copolymer as toughening agent, and the main purpose is to reduce the crystallinity in the modified composite system, and the microstructure state of the ethylene-octene copolymer rubber phase is more effectively exerted when the surface layer of the hinge structure is in a stretched state, so that the ethylene-octene copolymer itself has good capability of bearing large deformation when the hinge structure bears large deformation of stretching and bending, and the requirement that the surface layer of the hinge structure is not broken is met.
The crystallinity of the components of the present invention is determined using the ISO 11357-2016 standard method.
The DSC testing method specifically comprises the following steps: and testing the DSC curve of the polymer to obtain the area surrounded by the melting curve and the base line, and converting the area into heat, namely the heat of fusion of a polymer crystallization part, wherein the heat of fusion of the polymer crystallization part is higher than the theoretical heat of fusion when the polymer crystallization part is crystallized by 100%, namely the crystallinity of the polymer.
Wherein the filler can be talcum powder and/or calcium carbonate.
In practical application, additives such as an antioxidant, a lubricant, toner and the like can be added according to the actual performance requirement.
Wherein, the toner also comprises 0 to 0.6 part of antioxidant, 0 to 0.2 part of lubricant and 0 to 1.5 parts of toner by weight.
The primary antioxidant can be selected from one or a mixture of several hindered phenol antioxidants.
The secondary antioxidant can be selected from one or a mixture of several of phosphite esters.
The hindered phenol antioxidant can be one or a mixture of more of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1024, antioxidant AO-330, etc.
The phosphite antioxidant can be one or a mixture of more of antioxidant 168, antioxidant 626, antioxidant 618 and antioxidant 398V.
The lubricant is one or more selected from silicone, esters, amides, polyethylene, stearic acid, fatty acid and esters.
The toner can be selected from carbon black and other toners according to the actual color requirement.
The antioxidant can improve the antioxidant effect of the folding-resistant polypropylene composite material, the lubricant can improve the lubricating effect of the folding-resistant polypropylene composite material, and the toner can dye the folding-resistant polypropylene composite material.
The invention also provides a preparation method of the folding-resistant polypropylene composite material, which specifically comprises the following steps: and uniformly mixing the components, performing melt extrusion and granulation at 160-220 ℃ by a double-screw extruder, and drying to obtain the folding-resistant polypropylene composite material.
The folding-resistant polypropylene composite material prepared by the invention has good elongation at break and mechanical properties, can be widely applied to the preparation of plastic products, and particularly protects the application of the folding-resistant polypropylene composite material in the preparation of plastic hinges.
The invention also particularly protects a hinge, and the plastic hinge is prepared from the folding-resistant polypropylene composite material.
Preferably, the plastic hinge has a wall thickness of 0.2-0.5 mm.
The plastic hinge of the invention can be prepared by injection molding.
Compared with the prior art, the invention has the beneficial effects that:
the folding-resistant polypropylene composite material can realize the improvement of the elongation at break through the optimized synergistic effect of the resin base material, does not influence other physical and mechanical properties, can not crack when repeatedly folding the surface layer in the continuous use process of the hinge structure workpiece, and has good appearance.
The breaking elongation of the plastic hinge prepared from the folding-resistant polypropylene composite material can reach up to 525%, and the surface layer is not damaged when the plastic hinge is repeatedly folded for 10 times to 7 times.
Drawings
FIG. 1 is an appearance of a plastic hinge without cracking the skin.
Fig. 2 shows the appearance of a broken plastic hinge skin.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Metallocene polypropylene 1 is mPP MH7700, and has a molecular weight distribution index M w /M n 2.4, a crystallinity of 35%, a melt mass flow rate of 25g/10min, a flexural modulus of 1550MPa, a notched Izod impact strength of 3.0kJ/m 2 Korean LG chemistry;
the metallocene polypropylene 2 is mPP MR10MX0, and the molecular weight distribution index M w /M n 2.3, crystallinity of 32%, melt mass flow rate of 10g/10min, flexural modulus of 1300MPa, notched Izod impact strength of 5kJ/m 2 Korean daol company;
the metallocene polypropylene 3 is mPP MH1700 and has a molecular weight distribution index M w /M n 2.7, a crystallinity of 38%, a melt mass flow rate of 40g/10min, a flexural modulus of 1550MPa, a notched Izod impact strength of 3.0kJ/m 2 Korean LG chemistry;
the metallocene polypropylene 4 is mPP JHM2002, and the molecular weight distribution index M w /M n 2.4, a crystallinity of 34%, a melt mass flow rate of 20g/10min, a flexural modulus of 1250MPa, and a notched Izod impact strength of 5kJ/m 2 Shandong jingcheng petrochemical products;
the metallocene polypropylene 5 is mPP HM562S, and the molecular weight distribution index M w /M n 2.4, 36% crystallinity, 30g/10min melt mass flow rate, 1300MPa flexural modulus, and 4.0kJ/m notched Izod impact strength 2 LyondellBasell industries, inc;
metallocene polypropylene6 is mPP WMG03UX, molecular weight distribution index M w /M n 3.0, 40% crystallinity, 30g/10min melt mass flow rate, 1450MPa flexural modulus, 3.5kJ/m notched Izod impact strength 2 JPP corporation, japan;
the metallocene polypropylene 7 is mPP MR30MX0, and the molecular weight distribution index M w /M n 2.0, a crystallinity of 35%, a melt mass flow rate of 30g/10min, a flexural modulus of 1250MPa, and a notched Izod impact strength of 5kJ/m 2 Korean daol company;
the metallocene polypropylene 8 is mPP WFW4M, and the molecular weight distribution index M w /M n 3.0, a crystallinity of 35%, a melt mass flow rate of 8g/10min, a flexural modulus of 1050MPa, and a notched Izod impact strength of 6.0kJ/m 2 JPP corporation, japan;
the metallocene polypropylene 9 is mPP M3720WZ and has a molecular weight distribution index M w /M n 2.4, a crystallinity of 28%, a melt mass flow rate of 24g/10min, a flexural modulus of 1450MPa, and a notched Izod impact strength of 3.0kJ/m 2 Korean daol company;
the metallocene polypropylene 10 is mPP MH1850 and has a molecular weight distribution index M w /M n 2.4, a crystallinity of 40%, a melt mass flow rate of 60g/10min, a flexural modulus of 2000MPa, and a notched Izod impact strength of 3.0kJ/m 2 Korean LG chemistry;
the impact copolymer polypropylene 1 is PP SP179 with a molecular weight distribution index M w /M n 4.0, crystallinity of 35%, mass content of ethylene propylene rubber of 27%, and notched impact strength of cantilever beam of 45kJ/m 2 The mass flow rate of the melt is 10g/10min, the flexural modulus is 850MPa, and the China petrochemical company is Qilu division;
the impact copolymer polypropylene 2 is PP 1120D, and the molecular weight distribution index M w /M n 3.9, crystallinity of 31%, mass content of ethylene propylene rubber of 15%, notched Izod impact strength of 28kJ/m 2 The melt mass flow rate is 15g/10min, the flexural modulus is 1475MPa, and Taiwan plastics industry Co., ltd;
the impact copolymer polypropylene 3 is PP 1692, and the molecular weight distribution index M w /M n 4.4, crystallinity of 37%, mass content of ethylene propylene rubber of 30%, notched Izod impact strength of 53kJ/m 2 The melt mass flow rate was 20g/10min, the flexural modulus was 1000MPa, liande Bassell Industrial Co;
the impact copolymer polypropylene 4 is PP K9017, and the molecular weight distribution index M w /M n 4.0, crystallinity of 33.7%, mass content of ethylene propylene rubber of 29%, and notched Izod impact strength of 50kJ/m 2 The melt mass flow rate is 16g/10min, the flexural modulus is 900MPa, taiwan plastics industry Co., ltd;
the impact copolymer polypropylene 5 is PP K9829H, and the molecular weight distribution index M w /M n 4.3, crystallinity of 35.3%, mass content of ethylene propylene rubber of 25%, and notched impact strength of cantilever beam of 35kJ/m 2 The mass flow rate of the melt is 28g/10min, the flexural modulus is 1030MPa, and the China petrochemical Yanshan division company;
the impact copolymer polypropylene 6 is PP 2-9301, and the molecular weight distribution index M w /M n 3.5, crystallinity of 40%, mass content of ethylene propylene rubber of 40%, notched Izod impact strength of 60kJ/m 2 The melt mass flow rate is 30g/10min, the flexural modulus is 1100MPa, inno-Comp Kft company;
the impact copolymer polypropylene 7 is PP 511MK40T, and the molecular weight distribution index M w /M n 4.0, crystallinity of 35.8%, mass content of ethylene propylene rubber of 10%, notched impact strength of cantilever beam of 10kJ/m 2 The melt mass flow rate was 30g/10min, the flexural modulus was 1250MPa, and the sand foundation industry company;
the impact copolymer polypropylene 8 is PP 6630A, and the molecular weight distribution index M w /M n 4.0, crystallinity of 32.4%, mass content of ethylene propylene rubber of 35%, and notched impact strength of cantilever beam of 55kJ/m 2 The melt mass flow rate is 30g/10min, the flexural modulus is 1250MPa, and Taiwan plastics industry Co., ltd;
the impact copolymer polypropylene 9 is PP 3208, and the molecular weight distribution index M w /M n 4.0, crystallinity of 28.7%, mass content of ethylene propylene rubber of 22%, notched Izod impact strength of 32kJ/m 2 The melt mass flow rate was 10g/10min, the flexural modulus was 1070MPa, pinnacle polymer Co., ltd;
the impact copolymer polypropylene 10 is PP 6510E, and has a molecular weight distribution index M w /M n 4.1, crystallinity of 38.5%, mass content of ethylene propylene rubber of 17%, notched Izod impact strength of 21kJ/m 2 The melt mass flow rate is 10g/10min, the flexural modulus is 1500MPa, taiwan plastics industry Co., ltd;
the impact copolymer polypropylene 11 is PP CMR648, the molecular weight distribution index M w /M n 3.7, crystallinity of 36.4%, mass content of ethylene propylene rubber of 28.5%, and notched Izod impact strength of 50kJ/m 2 The melt mass flow rate was 10g/10min, the flexural modulus was 1050MPa, sasol polymers Co., ltd;
the impact copolymer polypropylene 12 is PP BNU013, and has a molecular weight distribution index M w /M n 4.6, crystallinity of 35.7%, mass content of ethylene propylene rubber of 17%, notched Izod impact strength of 25kJ/m 2 The melt mass flow rate is 22g/10min, the flexural modulus is 1030MPa, and the Ekksen Mobil chemical Co., ltd;
the thermoplastic elastomer 1 is an ethylene-octene copolymer POE LC565 with crystallinity of 4.3% and LG chemical enterprises limited company;
the thermoplastic elastomer 2 is ethylene-octene copolymer POE LC150 with crystallinity of 3% and LG chemical company Limited;
the thermoplastic elastomer 3 is an ethylene-octene copolymer POE 8150 with a crystallinity of 6% and is manufactured by Dow chemical company;
the thermoplastic elastomer 4 is an ethylene-octene copolymer POE 8180 with a crystallinity of 2% and is manufactured by Dow chemical company;
the thermoplastic elastomer 5 is an ethylene-octene copolymer POE XLT 8677 with a crystallinity of 10% and is manufactured by Dow chemical company;
fillers, talc, commercially available and used in the same way as the examples and comparative examples;
the mass ratio of the antioxidant to the hindered phenol antioxidant to the phosphite antioxidant is 1:1, and the hindered phenol antioxidant and the phosphite antioxidant are sold in the market and are the same in the examples and the comparative examples;
lubricants, amide-based lubricants, are commercially available and are the same for the examples and comparative examples;
the toner, carbon black masterbatch, are commercially available and the same is used for the examples and comparative examples.
Examples 1 to 18
The folding-resistant polypropylene composite material comprises the following components in parts by weight:
metallocene polypropylene; an impact copolymer polypropylene; fillers and thermoplastic elastomers;
wherein the specific contents of the components are shown in Table 1 below.
Table 1 composition (in parts by weight) of the folding-resistant polypropylene composite material of each example
| Component (A) | 1 | 2 | 3 | 4 | 5 | 6 |
| Metallocene Polypropylene 1 | 48 | 40 | 60 | 45 | 50 | 48 |
| Impact copolymer polypropylene 1 | 26 | 30 | 10 | 28 | 25 | 26 |
| Packing material | 26 | 30 | 20 | 28 | 25 | 26 |
| Thermoplastic elastomer 1 | 6.5 | 5 | 10 | 7 | 6 | 6.5 |
| Antioxidant | 0.6 | 0.6 | 0.3 | 0.6 | 0.6 | |
| Lubricant | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
Table 1, below
The preparation method of the folding-resistant polypropylene composite material comprises the following steps:
uniformly mixing the components, performing melt extrusion and granulation at 160-220 ℃ by a double-screw extruder, and drying to obtain the folding-resistant polypropylene composite material;
wherein the length-diameter ratio of the twin-screw extruder is (36-48) 1, the processing temperature is 160-220 ℃, the screw rotating speed is 400-650 rpm, and the feeding amount is 300-1000 kg/h.
Comparative examples 1 to 18
The folding-resistant polypropylene composite material comprises the following components in parts by weight:
metallocene polypropylene; an impact copolymer polypropylene; fillers and thermoplastic elastomers, wherein the specific amounts of the components are shown in table 2 below.
Table 2 composition (in parts by weight) of the folding-resistant polypropylene composite material of each comparative example
| Component (A) | 1 | 2 | 3 | 4 | 5 | 6 |
| Metallocene Polypropylene 1 | 48 | 48 | 48 | 30 | 70 | |
| Impact copolymer polypropylene 1 | 5 | 40 | 26 | 26 | 26 | |
| Packing material | 26 | 26 | 26 | 26 | 26 | 26 |
| Thermoplastic elastomer 1 | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 |
| Antioxidant | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 |
| Lubricant | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
Continuous table 2
The preparation method of the folding-resistant polypropylene composite material comprises the following steps:
uniformly mixing the components, performing melt extrusion and granulation at 160-220 ℃ by a double-screw extruder, and drying to obtain the folding-resistant polypropylene composite material;
wherein the length-diameter ratio of the twin-screw extruder is (36-48) 1, the processing temperature is 160-220 ℃, the screw rotating speed is 400-650 rpm, and the feeding amount is 300-1000 kg/h.
Result detection
Elongation at break, test standard is ISO 527-2:2012, test conditions are 50mm/min;
the notched impact strength of the cantilever beam is tested according to ISO180-2000, and the test condition is 23 ℃/1A;
appearance detection, folding for 10-7 times, wherein the surface layer is not broken and is not broken.
The specific test results for each example are set forth in Table 3 below:
table 3 shows the sequence
The specific test results of each comparative example are shown in table 4 below.
Continuous table 4
From the data, the breaking elongation of the plastic hinge prepared from the folding-resistant polypropylene composite material can reach up to 525%, and the surface layer is not damaged after repeated folding for 10 to 7 times, and the cantilever impact strength is improved.
As can be seen from the above comparative example 1 and example 1, the elongation at break was far from 525% without adding the impact copolymer polypropylene, and the skin was broken and the appearance test was not passed.
As can be seen from the above comparative example 7 and example 1, the metallocene polypropylene has an excessively wide molecular weight distribution index Mw/Mn and an excessively high crystallinity, and adversely affects the elongation at break and the notched impact strength at ordinary temperatures. When the molecular weight distribution index is higher, the content of the small molecular weight chain segments contained in the metallocene PP is higher, and from the aspect of molecular chain unwrapping, the small molecular weight molecular chains are easier to unwrap, so that the value of the elongation at break is lower, and the phenomenon that the surface layer of the hinge structure is broken after repeated folding for many times is shown. When the crystallinity is too high, the amorphous region in the metallocene PP naturally decreases, so that the molecular chain stretching orientation trend on the microcosmic scale becomes weaker, the macroscopic elongation at break is lower, and the molecular chain structure is broken after repeated folding for a plurality of times.
As can be seen from the above comparative example 12 and example 1, the molecular weight distribution index Mw/Mn of the impact copolymer polypropylene is too narrow and the crystallinity is too high, and from the viewpoint of the impact copolymer polypropylene, the polypropylene with narrow molecular weight distribution and high ethylene propylene rubber content is used as one of the components in the comparative example, but the impact copolymer polypropylene has higher crystallinity, and the impact copolymer polypropylene has higher crystallinity and does not have good effect on the improvement and stabilization of macroscopic elongation at break, which means that the indexes of the molecular weight distribution index, the crystallinity and the ethylene propylene rubber content of the impact copolymer polypropylene determined by the invention need to be controlled within a certain range, but not all three are as high as possible.
As can be seen from comparative examples 7 to 18, the respective properties of the metallocene polypropylene and the impact copolymer polypropylene are not within the scope of the present invention, and the effect of the present invention cannot be achieved.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (9)
1. The folding-resistant polypropylene composite material is characterized by comprising the following components in parts by weight:
40-60 parts of metallocene polypropylene;
10-30 parts of impact copolymer polypropylene;
20-30 parts of filler;
5-10 parts of thermoplastic elastomer;
0-3 parts of an auxiliary agent;
the molecular weight distribution index Mw/Mn of the metallocene polypropylene is 2.3-2.7, the crystallinity is 32-38%, and the test standard of the crystallinity is ISO 11357-2016;
the molecular weight distribution index Mw/Mn of the impact copolymer polypropylene is 3.9-4.4, the crystallinity is 31-37%, the test standard of the crystallinity is ISO 11357-2016, and the mass content of ethylene propylene rubber in the impact copolymer polypropylene is 15-30%;
the thermoplastic elastomer is an ethylene-octene copolymer, the crystallinity of the thermoplastic elastomer is 3-6%, and the test standard of the crystallinity is ISO 11357-2016.
2. The folding-resistant polypropylene composite material according to claim 1, comprising the following components in parts by weight:
45-50 parts of metallocene polypropylene;
25-28 parts of impact copolymer polypropylene;
25-28 parts of filler;
6-7 parts of thermoplastic elastomer;
0.8-1.8 parts of auxiliary agent;
the auxiliary agent is one or more of antioxidant, lubricant or toner.
3. The fold-resistant polypropylene composite material according to claim 1, wherein the metallocene polypropylene has a crystallinity of 34 to 36%.
4. The folding-resistant polypropylene composite material according to claim 1, wherein the crystallinity of the impact copolymer polypropylene is 32-35%, and the mass content of the ethylene propylene rubber in the impact copolymer polypropylene is 25-30%.
5. The folding-resistant polypropylene composite material according to claim 1, wherein the metallocene polypropylene has a melt mass flow rate of 20-30 g/10min, a test standard of ISO1133-2011, and a test condition of 230 ℃ and 2.16kg.
6. The fold-resistant polypropylene composite material according to claim 5, wherein the impact copolymer polypropylene has a notched izod impact strength of 30 to 50kj/m 2 The test standard is ISO180-2000, and the test temperature is 23 ℃.
7. The method for preparing the folding-resistant polypropylene composite material according to any one of claims 1 to 6, which is characterized by comprising the following steps:
and uniformly mixing the components, performing melt extrusion and granulation at 160-220 ℃ by a double-screw extruder, and drying to obtain the folding-resistant polypropylene composite material.
8. Use of the fold-resistant polypropylene composite material according to any one of claims 1 to 6 for the preparation of plastic hinges.
9. A plastic hinge, characterized in that the plastic hinge is prepared from the folding-resistant polypropylene composite material according to any one of claims 1 to 6.
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| CN115895103A (en) * | 2022-09-15 | 2023-04-04 | 兰州理工大学 | Method for modifying common polypropylene into polypropylene with high impact resistance |
| CN117567810A (en) * | 2024-01-16 | 2024-02-20 | 新疆独山子石油化工有限公司 | Multifunctional metallocene polyethylene and its compound additive and preparation method |
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| CN114479266B (en) * | 2021-12-21 | 2023-05-05 | 天津金发新材料有限公司 | Folding-resistant polypropylene composite material and preparation method and application thereof |
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| CN102206376A (en) * | 2010-03-31 | 2011-10-05 | 上海金发科技发展有限公司 | Polypropylene material filled with inorganic mineral powder, and its preparation method and application |
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